Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
  • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
  • G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
  • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/40—Treatment after imagewise removal, e.g. baking
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
  • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

• the present invention relates to a positive photosensitive resin composition and a cured film obtained therefrom. More specifically, the present invention relates to a positive photosensitive resin composition capable of forming an image having high water repellency and oil repellency on the surface of the cured film, a cured film thereof, and various materials using the cured film.
• This positive photosensitive resin composition is particularly suitable for use as an interlayer insulating film in a liquid crystal display or an EL display, a light shielding material corresponding to an inkjet method, or a partition material.
• a patterned electrode protective film As a material for forming these films, among the photosensitive resin compositions, there are photosensitive resin compositions having a feature that the number of steps for obtaining a required pattern shape is small and sufficient flatness is provided. Have been widely used.
• the substrate can be made hydrophilic and the bank can be made water repellent by continuous plasma (ozone) treatment such as oxygen gas plasma treatment and fluorine gas plasma treatment.
• ozone continuous plasma
• the process is complicated.
• proposals have been made in which a photosensitive organic thin film is blended with a fluorosurfactant or a fluoropolymer (see, for example, Patent Document 4).
• the UV ozone treatment during the hydrophilic treatment of the substrate reduces the water repellency of the surface, which is not practical.
• JP 2000-187111 A Japanese Patent Laid-Open No. 11-54270 JP 2000-353594 A JP-A-10-197715
• the present invention has been made in view of the above circumstances, and the problem to be solved is used for liquid crystal display elements, organic EL display elements and the like, and has high water repellency on the surface of a cured film even after treatment with plasma or the like. It is to form an image of a cured film having high oil repellency and insulating properties. In particular, it is to form an image of a cured film that can prevent a situation where an ink droplet overflows to an adjacent pixel beyond a bank in manufacturing a substrate using inkjet.
• TFT-type liquid crystal display elements and organic EL elements are also very important in terms of economic efficiency in the production process, and therefore, recycling of element substrates is required. That is, after a pattern film is formed from the photosensitive resin composition, when a pattern is inspected and a defect has occurred, it is required that the rework process of removing the pattern film from the substrate and collecting the substrate can be easily performed. .
• a cured film obtained from a conventionally proposed positive photosensitive resin composition is rather intended to be insolubilized in an organic solvent or the like after post-baking to reduce film loss.
• the intended purpose is not necessarily achieved.
• the present invention has been made in view of these circumstances, and maintains a good image without causing reflow or the like during film curing, and a positive photosensitive resin composition having a cured film having good reworkability. For the purpose of provision.
• the inventors of the present invention formed a cured film from a composition containing an acrylic polymer having a fluoroalkyl group and a silyl ether group, whereby water repellency and liquid repellency were formed on the film surface. It has been found that good reworkability can be imparted by introducing a group capable of being efficiently imparted to the acrylic polymer and dissociating by the action of an acid into the acrylic polymer.
• this invention relates to the positive photosensitive resin composition containing the following (A) component, (B) component, (C) component, and (D) component as a 1st viewpoint.
• (A) component an acrylic polymer having an acid dissociable group, an aliphatic hydroxyl group and an N-substituted maleimide group
• (B) component an acrylic polymer having an acid dissociable group and a block isocyanate group
• Component (D) a photoacid generator.
• the positive type according to the first aspect wherein the acid dissociable groups in the component (A), the component (B) and the component (C) are each independently an alkoxyalkyl group having 2 to 11 carbon atoms.
• the present invention relates to a photosensitive resin composition.
• the (A) component is an acrylic polymer having an acid dissociable group, an aliphatic hydroxyl group, and an N-substituted maleimide group in a molar ratio of 5 to 50: 5 to 50:20 to 70.
• the present invention relates to the positive photosensitive resin composition described in the second aspect.
• the component (B) is an acrylic polymer having an acid dissociable group and a block isocyanate group in a molar ratio of 5 to 50:15 to 80, and any one of the first aspect to the third aspect
• the component (C) contains an acid dissociable group, an aliphatic hydroxyl group, a fluoroalkyl group having 3 to 10 carbon atoms, and a silyl ether group in a range of 5 to 40: 5 to 50: 5 to 50:10 to 60 It is related with the positive photosensitive resin composition as described in any one of the 1st viewpoint thru
• the positive electrode according to any one of the first to sixth aspects containing 0.05 to 10 parts by mass of a siloxane compound as a component (E) based on 100 parts by mass of the component (A).
• Type photosensitive resin composition based on 100 parts by mass of component (A).
• the compound (F) contains 0.5 to 10 parts by mass of a compound having two or more vinyl ether groups in one molecule based on 100 parts by mass of the component (A).
• the positive photosensitive resin composition according to any one of the aspects.
• the present invention relates to a resin composition.
• (A) component an acrylic polymer obtained by polymerizing a monomer mixture containing a monomer having an acid-dissociable group, a monomer having an aliphatic hydroxyl group, and an N-substituted maleimide monomer;
• (B) component an acrylic polymer obtained by polymerizing a monomer mixture containing a monomer having an acid-dissociable group and a monomer having a block isocyanate group,
• a thirteenth aspect is a method of forming an image by applying a photosensitive resin composition to a substrate to form a film, and then performing exposure and development, wherein the resin composition comprises the first to ninth aspects.
• PEB post-exposure heating
• the present invention relates to the image forming method according to the thirteenth aspect, further including a step of heating (post-baking) at a temperature of 130 to 250 ° C. after development.
• the positive photosensitive resin composition of the present invention is suitable as a material for forming a patterned insulating film used for a liquid crystal display element, an organic EL display element, or the like, or a pixel interval wall material.
• a material for forming a patterned insulating film used for a liquid crystal display element, an organic EL display element, or the like, or a pixel interval wall material Has good reworkability, and maintains a good image even after being cured, and can maintain high water repellency and high oil repellency after treatment with oxygen plasma (ozone) or the like.
• the cured film obtained using the positive photosensitive resin composition of the present invention can prevent a situation in which ink droplets overflow to the adjacent pixels beyond the bank in the substrate production using the ink jet.
• Various elements and materials made using such a cured film can be provided.
• the positive photosensitive resin composition of the present invention contains (A) to (C) component acrylic polymers and (D) component photoacid generators, and (E) component siloxane, if desired.
• the compound is a composition containing a compound having two or more vinyl ether groups in one molecule of the component (F).
• the composition of the present invention can form a film in which the fluoroalkyl group having 3 to 10 carbon atoms and the silyl ether group are unevenly distributed in the vicinity of the surface by containing the acrylic polymer of the component (C). Thereby, water repellency and liquid repellency can be efficiently provided to the film surface.
• the acrylic polymers of the components (A) to (C) it is possible to achieve good reworkability and maintain a good image without causing reflow during curing.
• details of each component will be described.
• the component (A) is an acrylic polymer having an acid dissociable group, an aliphatic hydroxyl group and an N-substituted maleimide group.
• the acid dissociable group means a group that dissociates from an acrylic polymer by the action of an acid generated from a photoacid generator, which will be described later.
• the alkyl group preferably has 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.
• the alkoxy group here preferably has 1 to 6 carbon atoms.
• alkoxyalkyl groups include methoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, isopropoxyethyl group, isopropoxyethyl group, butoxyethyl group, isobutoxyethyl group, t-butoxyethyl group, And a cyclohexyloxyethyl group.
• t-alkyl group include a t-butyl group and a t-amyl group.
• bridged cyclic hydrocarbon group include a norbornenyl group, a 2-methyladamantyl group, and a 1-methyladamantyl group.
• alkoxycarbonyl group include a t-butoxycarbonyl group.
• the above-mentioned aliphatic hydroxyl group includes a hydroxyalkyl group, preferably a hydroxyalkyl group having 2 to 10 carbon atoms, more preferably a hydroxyalkyl group having 2 to 10 carbon atoms.
• the N-substituted maleimide group is a group in which the N atom of the maleimide group is substituted with an organic group, and examples of the substituent in the N atom include an alicyclic group, an alkyl group, and a phenyl group. Specific examples include a cyclohexyl group, an alkyl group having 1 to 5 carbon atoms, and a phenyl group. An alicyclic group or an alkyl group is preferable.
• the molar ratio of acid dissociable group: aliphatic hydroxyl group: N-substituted maleimide group is preferably 5 to 50: 5 to 50:20 to 70, more preferably 10 Thru 40:10 thru 40:30 thru 60.
• the number average molecular weight of the acrylic polymer as the component (A) is preferably 1,500 to 20,000.
• the acrylic polymer of the component (A) includes a monomer having an acid dissociable group, a monomer having an aliphatic hydroxyl group, an N-substituted maleimide monomer, and, if desired, other than the above. It can be obtained by subjecting a monomer (hereinafter also referred to as other monomer A) to a polymerization reaction at a temperature of 50 to 110 ° C. in a solvent in the presence of a polymerization initiator.
• the acrylic A thus obtained is usually in the form of a solution in which the acrylic A is dissolved in a solvent. In this state (without isolation), the acrylic A can be used for the positive photosensitive resin composition of the present invention. it can.
• the acrylic A solution obtained as described above was re-precipitated by stirring with stirring such as diethyl ether or water, and the generated precipitate was filtered and washed, and then under normal pressure or reduced pressure, Acrylic A powder can be obtained by drying at room temperature or by heating. By such an operation, the polymerization initiator and unreacted monomer coexisting with acrylic A can be removed, and as a result, purified acrylic A powder can be obtained. If sufficient purification cannot be achieved by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
• the acrylic A powder may be used as it is, or the powder may be redissolved in, for example, a solvent described later and used as a solution.
• Examples of the monomer having a dissociable group include 1-methoxyethyl methacrylate, 1-methoxyethyl acrylate, 1-ethoxyethyl methacrylate, 1-ethoxyethyl acrylate, 1-propoxyethyl methacrylate, 1-propoxyethyl acrylate, 1-isopropoxy Ethyl methacrylate, 1-isopropoxyethyl acrylate, 1-butoxyethyl methacrylate, 1-butoxyethyl acrylate, 1-isobutoxyethyl methacrylate, 1-isobutoxyethyl acrylate, 1-t-butoxyethyl methacrylate, 1-t-butoxyethyl Acrylate, 1-cyclohexyloxyethyl methacrylate, 1-cyclohexyloxyethyl acrylate, methoxymethyl methacrylate, methoxymethyl Acrylate, ethoxymethyl methacrylate, ethoxy
• Examples of the monomer having an aliphatic hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, and glycerol methacrylate. Is mentioned.
• N-substituted maleimide monomers examples include N-ethylmaleimide, N-methylmaleimide, N-phenylmaleimide, N-benzylmaleimide, and N-cyclohexylmaleimide.
• Examples of the other monomer A include methacrylic acid, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methoxytrile.
• polymerization initiator examples include ⁇ , ⁇ ′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4- Dimethylvaleronitrile), dimethyl-2,2′-azobis (2-methylpropionate), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile) ), 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 1- (1-cyano-1-methylethylazo) formamide, 2,2′-azobis (N-butyl-) 2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide), di-o-methylbenzoyl peroxide, di-p-methylben
• examples thereof include zoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-d
• a solvent (hereinafter also referred to as a polymerization solvent) used in the production of the acrylic A is not particularly limited as long as each monomer constituting the acrylic A and the acrylic A are dissolved.
• Component (B) is an acrylic polymer having an acid dissociable group and a block isocyanate group.
• As said acid dissociable group the same thing as the acid dissociable group quoted in the above-mentioned (A) component can be mentioned.
• the above-mentioned blocked isocyanate group means a group in which an isocyanate group (—NCO) is blocked with an appropriate protecting group, that is, a group obtained by reacting an isocyanate group with a blocking agent.
• the protecting group (block portion) is dissociated by thermal dissociation at a high temperature to generate an isocyanate group, where the protecting group is preferably dissociated from the isocyanate group at 140 ° C. or higher.
• blocking agents include oximes such as methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, diisobutyl ketone oxime, acetone oxime, butanal oxime, acetaldehyde oxime, and lactams such as epsilon caprolactam and heptanolactam.
• oximes such as methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, diisobutyl ketone oxime, acetone oxime, butanal oxime, acetaldehyde oxime, and lactams such as epsilon caprolactam and heptanolactam.
• lactams such as epsilon caprolactam and heptanolactam.
• the molar ratio of acid dissociable group: block isocyanate group is preferably 5 to 50:15 to 80.
• the number average molecular weight of the acrylic polymer as the component (B) is preferably 2,000 to 30,000.
• the method for producing the acrylic polymer of the component (B) (hereinafter also simply referred to as acrylic B) is the same as the method for producing the acrylic polymer of the component (A), that is, a monomer having an acid dissociable group. And a monomer having a block isocyanate group and, if desired, a monomer other than the above (hereinafter also referred to as other monomer B) in a solvent in the presence of a polymerization initiator at a temperature of 50 to 110 ° C. can get.
• the acrylic B thus obtained is usually in the form of a solution in which the acrylic B is dissolved in a solvent. In this state (without isolation), the acrylic B can be used for the positive photosensitive resin composition of the present invention. it can.
• the acrylic B solution obtained as described above is subjected to reprecipitation, filtration / washing of the precipitate, normal temperature or reduced pressure at normal temperature or under reduced pressure as needed, similar to the acrylic A solution.
• a purified acrylic B powder can be obtained.
• the acrylic B powder may be used as it is, or the powder may be redissolved in, for example, a solvent described later and used as a solution.
• the same ones as used in the method for producing acrylic A can be used.
• the other monomer B can use the same thing as the monomer and the other monomer A which have the aliphatic hydroxyl group used with the manufacturing method of the said acrylic A.
• the monomer having a block isocyanate group include isocyanate-containing monomers such as isocyanate ethyl methacrylate, isocyanate ethyl acrylate, m-tetramethylstyrene isocyanate, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, diisobutyl ketone oxime, Acetone oxime, butanal oxime, acetaldehyde oxime, epsilon caprolactam, heptanolactam, phenols such as phenol and cresol, and monomers added with blocking agents such as pyrazole, 3,5-dimethylpyrazole, or 3-methylpyrazole .
• isocyanate-containing monomers such as isocyanate ethyl methacrylate, isocyanate ethyl acrylate, m-tetramethylsty
• Component (C) is an acrylic polymer having an acid dissociable group, an aliphatic hydroxyl group, a fluoroalkyl group having 3 to 10 carbon atoms, and a silyl ether group.
• an acid dissociable group and aliphatic hydroxyl group the same thing as the acid dissociable group and aliphatic hydroxyl group mentioned in the above-mentioned (A) component can be mentioned.
• the fluoroalkyl group has 3 to 10 carbon atoms, preferably a fluoroalkyl group having 4 to 10 carbon atoms.
• a fluoroalkyl group examples include 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2- (perfluorobutyl) ethyl group, and 3-perfluorobutyl.
• the silyl ether group means a group in which a hydroxy group of an alcohol is protected with a trialkylsilyl group, and is preferably a group represented by the following formula. -X 4 -Si (O-SiX 1 X 2 X 3 ) 3 (Wherein X 1 , X 2 and X 3 each independently represents an alkyl group having 1 to 3 carbon atoms, and X 4 represents an alkylene group having 1 to 6 carbon atoms.)
• the molar ratio of acid dissociable group: aliphatic hydroxyl group: fluoroalkyl group: silyl ether group is 5 to 40: 5 to 50: 5 to 50:10 to 60. Is preferred.
• the number average molecular weight of the acrylic polymer as the component (C) is preferably 2,000 to 30,000.
• the method for producing the acrylic polymer of component (C) (hereinafter also simply referred to as acrylic C) is the same as the method for producing the acrylic polymer of component (A), that is, a monomer having an acid dissociable group.
• the acrylic C thus obtained is usually in the form of a solution in which the acrylic C is dissolved in a solvent, and can be used in this state (without isolation) for the positive photosensitive resin composition of the present invention. it can.
• the acrylic C solution obtained as described above is re-precipitation, filtration / washing of precipitates, and repeated at room temperature or under reduced pressure at normal temperature or reduced pressure as necessary, like the acrylic A solution.
• a purified acrylic C powder can be obtained.
• the acrylic C powder may be used as it is, or the powder may be redissolved in, for example, a solvent described later and used as a solution.
• the monomer having an acid-dissociable group the monomer having an aliphatic hydroxyl group, the polymerization initiator and the solvent used in the method for producing acrylic C, the same ones as used in the method for producing acrylic A can be used.
• the monomer having a fluoroalkyl group having 3 to 10 carbon atoms include 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3, 3-pentafluoropropyl acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2- (perfluorobutyl) ethyl acrylate, 2- (perfluorobutyl) ethyl methacrylate, 3-perfluorobutyl-2- Hydroxypropyl acrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2- (perfluorohexyl) ethyl acrylate, 2- (perfluorohexyl) ethyl methacrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 3- Pa Fluorohexyl-2-hydroxypropyl methacrylate, 2- (perflufluor
• Examples of the monomer having a silyl ether group include methacryloxypropyltris (trimethylsiloxy) silane, methacryloxytrispropylsilane, 2- (methacryloxyethoxy) trimethylsilane, 2- (methacryloxyethyl) trimethylsilane, and 2- (acryloxy). And ethoxy) trimethylsilane, acryloxytrispropylsilane, 2- (acryloxyethyl) trimethylsilane, and acryloxypropyltris (trimethylsiloxy) silane.
• the other monomer C may be the same as the other monomer A used in the method for producing the acrylic A, and among them, it may be a monomer having no alkali-soluble group (hydroxyphenyl group, carboxyl group). preferable.
• Specific examples of such other monomer C include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, Methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, ⁇ -butyrolactone methacrylate, 2-propy
• a component is a photo-acid generator (PAG). This is a substance that generates an acid (sulfonic acid, carboxylic acid, etc.) directly or indirectly by irradiation of light used for exposure. If it has such properties, its type and structure are There is no particular limitation.
• PAG photo-acid generator
• Examples of the photoacid generator of component (D) include diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzoin tosylate compounds, iron arene complexes, and halogen-containing triazines. Compounds, acetophenone derivative compounds, cyano group-containing oxime sulfonate compounds, and the like. Any conventionally known or conventionally used photoacid generator can be applied in the present invention without any particular limitation.
• the photo-acid generator of (D) component may be used individually by 1 type, and may be used in combination of 2 or more type.
• photoacid generator examples include the following. However, these compounds are examples of a very large number of applicable photoacid generators, and are of course not limited thereto.
• the photoacid generators it is preferable to use a compound that generates a strong acid by light, particularly a compound that generates sulfonic acid or hydrochloric acid.
• a siloxane compound may be used as the component (E).
• the siloxane compound as the component (E) is a series of heat treatment steps performed in the process of forming a cured film (pattern forming film) from the positive photosensitive resin composition of the present invention, that is, the acrylic weight of the component (A).
• the component (E) is a siloxane compound having a number average molecular weight of 100 to 2,000.
• the siloxane compound here refers to an organosiloxane compound, a compound in which a part thereof is substituted with a hydrogen atom or a hydroxy group, and a modified product thereof.
• siloxane compounds examples include linear siloxane compounds, siloxane compounds having a branched structure, cyclic siloxane compounds, and copolymers thereof.
• siloxane compounds modified with non-reactive groups such as alkoxy modification, polyether modification, fluorine modification, methylstyryl modification, higher fatty acid ester modification, hydrophilic special modification, higher alkoxy modification, and amino
• siloxane compounds modified with reactive groups such as modification, epoxy modification, carboxy modification, carbinol modification, methacryl modification, mercapto modification, and phenol modification.
• linear siloxanes such as polydimethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polymethylhydroxysiloxane, polymethylpropylsiloxane, polydiphenylsiloxane, polymethylbutylsiloxane, and copolymers thereof.
• Cyclic polydimethylsiloxane cyclic polymethylphenylsiloxane, cyclic polymethylhydroxysiloxane, cyclic polymethylethylsiloxane, cyclic polymethylpropylsiloxane, cyclic polymethylbutylsiloxane and other cyclic siloxanes, alkoxy-modified, polyether-modified, fluorine-modified, Non-reactive group-modified siloxane such as methylstyryl modification, higher fatty acid ester modification, hydrophilic special modification, higher alkoxy modification, amino modification, epoxy modification, carboxy Sex, carbinol-modified, methacryl-modified, mercapto-modified, reactive group-modified siloxane and copolymers thereof, such as phenol-modified, and the like.
• siloxane compounds can be easily obtained as commercial products. Specific examples thereof include L-45 (manufactured by Nippon Unicar Co., Ltd.), SH200, 510, 550, 710, 705, 1107 (Toray Manufactured by Dow Corning), X-22-162C, 3701E, 3710, 1821, 164S, 170DX, 176DX, 164A, 4952, KF96, 50, 54, 99, 351, 618, 910, 700, 6001, 6002, Linear siloxane compounds such as 8010, KR271, 282 (manufactured by Shin-Etsu Chemical Co., Ltd.), cyclic structures such as VS-7158 (manufactured by Nihon Unicar Co., Ltd.), BY11-003 (manufactured by Toray Dow Corning) Siloxane compounds, L-77, 720, 7001, 7604, Y-7006, L-9300, FZ-21 1, 2110, 2130, 2161,
• Modified siloxane compound FS1265 (manufactured by Toray Dow Corning), FL-5, FL-10, X-22-820, X-22-821, X-22-822, FL100 (Shin-Etsu Chemical Co., Ltd.) And a copolymer of polysiloxane and polyalkylene oxide such as FZ-2203, 2207, and 2222 (manufactured by Nippon Unicar Co., Ltd.).
• siloxane compounds a siloxane compound having a repeating unit having a structure represented by the formula (70) is particularly preferable.
• R 1 and R 2 are each independently a hydrogen atom, an alkyl group or a phenyl group, and p represents a positive integer.
• any siloxane compound having a repeating unit having the structure represented by the formula (70) may be modified or unmodified.
• the acid component generated from the photoacid generator of the component (D) described above may react with the epoxy group at the time of exposure, so that the siloxane compound does not have an epoxy group. Is preferred.
• Non-reactive groups such as unmodified siloxane compounds, alkoxy modified, polyether modified, fluorine modified, methyl styryl modified, higher fatty acid ester modified, hydrophilic special modified, higher alkoxy modified, etc.
• modified siloxane compounds and siloxane compounds modified with reactive groups such as amino modification, carboxy modification, carbinol modification, methacryl modification, mercapto modification, and phenol modification.
• siloxane compounds of component (E) unmodified siloxane compounds and carbinol-modified siloxane compounds are easily compatible with the acrylic polymer of component (A), and fluorine-modified siloxane compounds are It is preferable because oil repellency is obtained.
• the fluorine-modified siloxane compound mentioned here refers to the above-described organosiloxane compound, a compound in which a part thereof is substituted with a hydrogen atom or a hydroxy group, and a compound in which the modified product is further modified with fluorine.
• such a fluorine-modified siloxane compound is a siloxane compound in which R 1 and / or R 2 in the formula (70) is a fluoroalkyl group.
• the introduction amount of the fluoroalkyl group is preferably 10 to 100%, more preferably 20 to 80%.
• the introduction amount of the fluoroalkyl group is small, the oil repellency is lowered, and when the introduction amount of the fluoroalkyl group is too large, the resistance to UV-ozone treatment may be lowered.
• siloxane compound of the component (E) used in the present invention among the above-mentioned compounds, a carbinol-modified siloxane compound or a fluorine-modified siloxane compound, and a siloxane compound modified only with fluorine are more preferable.
• a fluorine-modified siloxane compound obtained by fluorine-modifying an unmodified siloxane compound, that is, a siloxane compound that has not been modified other than fluorine-modified is preferred.
• the siloxane compound (E) used in the present invention has compatibility with each component in the solution of the positive photosensitive resin composition of the present invention, particularly compatibility with the acrylic polymer of component (A).
• the positive photosensitive resin composition has good stability, solubility in a developer, water repellency of the upper surface portion of the remaining pattern which is a non-exposed region (light-shielding portion), and further, water repellency. From the viewpoint of imparting oiliness, a compound having a number average molecular weight of 100 to 2,000 is preferred.
• the compound (F) may further contain a compound having two or more vinyl ether groups in one molecule.
• Such component (F) has two or more vinyl ether groups in one molecule that can be thermally crosslinked with the acrylic polymer of component (A) at a conventional pre-baking temperature (eg, 80 ° C. to 150 ° C.). Any compound may be used, and the type and structure are not particularly limited.
• the compound of component (F) is separated from the acrylic polymer of component (A) by thermal crosslinking with the acrylic polymer of component (A) and then by acid generated by exposure in the presence of a photoacid generator. (Decrosslinking), and thereafter development using an alkaline developer together with the acrylic polymer of component (A) is removed.
• a vinyl ether compound generally used as a component of a vinyl ether type chemically amplified resist can be applied as this type of compound.
• the use of such a compound has the advantage that the shape of the formed film can be controlled by adjusting the thermal crosslinking density by changing the compounding amount of the compound.
• the compound especially represented by Formula (71) and Formula (72) is preferable at the point developed without the remaining film and residue in an exposure part. .
• n represents an integer of 2 to 10
• k represents an integer of 1 to 10
• R 3 represents an n-valent organic group.
• n represents an integer of 2 to 10.
• N in the formula (71) represents the number of vinyl ether groups in one molecule, and n is more preferably an integer of 2 to 4.
• m in formula (72) also represents the number of vinyl ether groups in one molecule, and m is more preferably an integer of 2 to 4.
• Specific examples of the compounds represented by formulas (71) and (72) include bis (4- (vinyloxymethyl) cyclohexylmethyl) glutarate, tri (ethylene glycol) divinyl ether, adipic acid divinyl ester, diethylene glycol divinyl ether. , Tris (4-vinyloxy) butyl trimellrate, bis (4- (vinyloxy) butyl) terephthalate, bis (4- (vinyloxy) butyl isophthalate, and cyclohexanedimethanol divinyl ether.
• the positive type photosensitive resin composition of the present invention can be used as necessary, as long as the effects of the present invention are not impaired, as a surfactant, a rheology modifier, an adhesion aid such as a silane coupling agent, a pigment, and a dye.
• a storage stabilizer, an antifoaming agent, or a dissolution accelerator such as a polyhydric phenol or a polycarboxylic acid can be contained.
• the positive photosensitive resin composition of the present invention comprises (A) an acrylic polymer, (B) an acrylic polymer, (C) an acrylic polymer, and (D) a photoacid generator.
• the siloxane compound as the component (E) the compound having two or more vinyl ether groups in one molecule of the component (F), and other additives, as desired. It is a composition which can further contain one or more of them.
• positive photosensitive resin composition of the present invention are as follows. [1]: Based on 100 parts by mass of component (A), 5 to 50 parts by mass of component (B), 0.5 to 30 parts by mass of component (C), and 0.1 to 20 parts by mass of ( D) Positive photosensitive resin composition containing a component. [2]: In the composition of [1] above, based on 100 parts by mass of component (A), 8 to 40 parts by mass of component (B), 1 to 20 parts by mass of component (C), or 0.5 Positive type photosensitive resin composition containing thru
• the siloxane compound as component (E) is used, it is preferably used at a ratio of 0.05 to 10 parts by mass with respect to 100 parts by mass of the acrylic polymer of component (A).
• the amount of the component (E) compound used exceeds the upper limit of the above range, whitening or film unevenness may occur during coating film formation.
• the proportion is 0.5 to 10 parts by mass with respect to 100 parts by mass of the acrylic polymer of the component (A). used.
• the amount of the compound (F) used exceeds the upper limit of the above range, the sensitivity of the film is greatly reduced, and residues between patterns are generated after development.
• the positive photosensitive resin composition of the present invention may be in a form dissolved in a solvent (component (G)).
• the solvent (G) may be any solvent that dissolves the components (A) to (D) and, if desired, the components (E), (F) and other additives. If it is a solvent having a function, its type and structure are not particularly limited. Examples of such a solvent (E) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol.
• solvents propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, etc. have good coating properties and safety Is preferable from the viewpoint of high.
• solvents are generally used as solvents for photoresist materials.
• the ratio of the solid content in the positive photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, and is, for example, 1 to 80% by mass. It is 5 to 60% by mass, or 10 to 50% by mass.
• solid content means what remove
• the preparation method of the positive photosensitive resin composition of this invention is not specifically limited, As the preparation method, (A) component is melt
• the solution of the acrylic polymer of component (A) to component (C) obtained at the time of producing the acrylic polymer of component (A) to component (C) is used as it is.
• a solvent may be further added for the purpose of adjusting the concentration.
• the solvent used in the preparation process of the acrylic polymer of the component (A) to the component (C) is the same as the solvent (G) used for adjusting the concentration when preparing the positive photosensitive resin composition. May be different or different.
• the prepared positive photosensitive resin composition solution is preferably used after being filtered using a filter having a pore size of about 0.2 ⁇ m.
• the positive photosensitive resin composition of the present invention is applied to a semiconductor substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, or an ITO substrate. Etc.) by spin coating, flow coating, roll coating, slit coating, spin coating following slit, ink jet coating, etc., and then pre-dried in a hot plate or oven to form a coating film can do. Then, a positive photosensitive resin film is formed by heat-treating this coating film.
• a semiconductor substrate for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, or an ITO substrate. Etc.
• a heating temperature and a heating time appropriately selected from the range of a temperature of 70 ° C. to 160 ° C. and a time of 0.3 to 60 minutes are employed.
• the heating temperature and heating time are preferably 80 to 140 ° C. and 0.5 to 10 minutes.
• the film thickness of the positive photosensitive resin film formed from the positive photosensitive resin composition is, for example, 0.1 to 30 ⁇ m, is, for example, 0.2 to 10 ⁇ m, and is further, for example, 0.2 to 5 ⁇ m. It is.
• the formed positive photosensitive resin film is hardly soluble in an alkaline developer by crosslinking the acrylic polymer of component (C) to the acrylic polymer of component (A) by heat treatment during formation. Become a film.
• the temperature of the heat treatment is lower than the lower limit of the above temperature range, the thermal crosslinking is insufficient, and the film may be reduced in the unexposed area.
• the temperature of the heat treatment exceeds the upper limit of the above temperature range and is too high, the once formed thermal bridge portion may be cut again to cause film reduction in the unexposed portion.
• the positive photosensitive resin film formed from the positive photosensitive resin composition of the present invention is exposed to light such as ultraviolet rays, ArF, KrF, and F 2 laser light using a mask having a predetermined pattern, Due to the action of the acid generated from the photoacid generator (PAG) of component (D) contained in the positive photosensitive resin film, the exposed portion of the film becomes soluble in an alkaline developer.
• light such as ultraviolet rays, ArF, KrF, and F 2 laser light using a mask having a predetermined pattern
• PEB post-exposure heating
• alkaline developer examples include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline.
• Alkaline aqueous solutions such as amine aqueous solutions such as ethanolamine, propylamine, and ethylenediamine. Further, a surfactant or the like can be added to these developers.
• a tetraethylammonium hydroxide 0.1 to 2.38 mass% aqueous solution is generally used as a photoresist developer, and this alkaline developer is also used in the positive photosensitive resin composition of the present invention. It can be used to develop well without causing problems such as swelling. Further, as a developing method, any of a liquid piling method, a dipping method, a rocking dipping method, and the like can be used. The development time at that time is usually 15 to 180 seconds.
• the positive photosensitive resin film is washed with running water, for example, for 20 to 90 seconds, and then air-dried with compressed air or compressed nitrogen or by spinning to remove moisture on the substrate, and A patterned film is obtained.
• the pattern forming film is subjected to post-baking for thermosetting, specifically by heating using a hot plate, an oven, etc., thereby providing heat resistance, transparency, and flatness.
• post-baking for thermosetting, specifically by heating using a hot plate, an oven, etc., thereby providing heat resistance, transparency, and flatness.
• a film having a good relief pattern with excellent water absorption and chemical resistance can be obtained.
• the post-bake is generally processed at a heating temperature selected from the range of 130 ° C. to 250 ° C. for 5 to 30 minutes when on a hot plate and 30 to 90 minutes when in an oven. The method is taken.
• a target cured film having a good pattern shape can be obtained.
• the positive photosensitive resin composition of the present invention can form a fine image with sufficiently high sensitivity and very small film thickness reduction in an unexposed portion during development.
• the film surface has high water repellency and high oil repellency, and it is possible to suppress a decrease in water repellency and oil repellency after oxygen plasma treatment (UV ozone treatment).
• solvents used for reworking include: glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether; methyl cellosolve acetate, ethyl Glycol esters such as cellosolve acetate, propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; glycols such as diethylene glycol, propylene glycol, butylene glycol and hexylene glycol; alcohols such as methanol, ethanol, 2-propanol and butanol; Acetone, methyl ethyl ketone, cyclopen Ketones such as non, cyclol
• HEMA 2-hydroxyethyl methacrylate MMA: methyl methacrylate
• CHMI N-cyclohexylmaleimide
• BEMA 1-butoxyethyl methacrylate
• MOI 2- (O- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate
• TMSSMA methacryloxy Propyltris (trimethylsiloxy) silane
• PFOMA 2- (perfluorooctyl) ethyl methacrylate
• PFHMA 2- (perfluorohexyl) ethyl methacrylate
• TFMMA trifluoromethyl methacrylate
• MAA methacrylic acid
• AIBN ⁇ , ⁇ '-azobisisobutyronitrile
• PAG1 oxime sulfonate photoacid
• Examples 1 to 7 and Comparative Examples 1 to 5> According to the composition shown in the following Table 3, the solution of the component (A), the solution of the component (B), the solution of the component (C), the component (D), the component (E), and the component (F) at a predetermined ratio ( G) A positive photosensitive resin composition of each example and each comparative example was prepared by dissolving in a solvent and stirring at room temperature for 3 hours to obtain a uniform solution.
• the positive photosensitive resin composition was applied onto a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a thickness of 2.5 ⁇ m.
• This coating film was immersed in a 0.4 mass% aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for 60 seconds, and then washed with running ultrapure water for 20 seconds. Next, this coating film was post-baked by heating at a temperature of 230 ° C. for 30 minutes to form a cured film having a thickness of 2.0 ⁇ m.
• TMAH tetramethylammonium hydroxide
• the positive photosensitive resin composition was applied onto a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a thickness of 2.5 ⁇ m.
• This coating film was immersed in a 0.4 mass% aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for 60 seconds, and then washed with running ultrapure water for 20 seconds. Next, this coating film was post-baked by heating at a temperature of 230 ° C. for 30 minutes to form a cured film having a thickness of 2.0 ⁇ m.
• TMAH tetramethylammonium hydroxide
• This cured film was subjected to ozone cleaning for 10 minutes using UV-312 manufactured by Technovision.
• the contact angles of water and anisole on the ozone-cleaned membrane were measured using a Drop Master manufactured by Kyowa Interface Science Co., Ltd. Table 4 shows the obtained results.
• the positive photosensitive resin composition was applied onto a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a thickness of 2.5 ⁇ m.
• This coating film was irradiated with UV light having a light intensity at 365 nm of 5.5 mW / cm 2 for a certain period of time through a mask of 20 ⁇ m line and space pattern by a UV irradiation apparatus PLA-600FA manufactured by Canon Inc., and then at a temperature of 110 ° C.
• Post exposure heating (PEB) was performed on a hot plate for 120 seconds.
• the film was developed by immersing in a 0.4% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds.
• the coating film on which the line and space pattern was formed was heated at 230 ° C. for 30 minutes to be post-baked and cured.
• the cross-sectional shape of the cured line and space pattern was observed using a scanning electron microscope S-4100 manufactured by Hitachi High-Technologies Corporation. Table 4 shows the obtained results.
• the positive photosensitive resin composition was applied onto a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a thickness of 2.5 ⁇ m.
• This coating film was immersed in a 0.4 mass% aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for 60 seconds, and then washed with running ultrapure water for 20 seconds. Next, this coating film was post-baked by heating at a temperature of 230 ° C. for 30 minutes to form a cured film having a thickness of 2.0 ⁇ m.
• TMAH tetramethylammonium hydroxide
• the cured film was immersed in N-methyl-2-pyrrolidone for 1 minute, and the film thickness was measured. A film with no change of 3% or more from the film thickness after post-baking showed a change of 3% or more. Was marked with x. Table 4 shows the obtained results.
• the positive photosensitive resin composition was applied onto a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a thickness of 2.5 ⁇ m.
• This coating film was irradiated with ultraviolet rays having a light intensity at 365 nm of 5.5 mW / cm 2 for a certain time by an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc., and then heated after exposure on a hot plate at a temperature of 110 ° C. for 120 seconds ( PEB).
• the film was developed by immersing in a 0.4% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds.
• the lowest exposure amount (mJ / cm 2 ) at which no undissolved portion remained in the exposed area was defined as sensitivity. Table 4 shows the obtained results.
• the positive photosensitive resin composition was applied onto a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a thickness of 2.5 ⁇ m.
• This coating film was irradiated with UV light having a light intensity at 365 nm of 5.5 mW / cm 2 for a certain period of time through a mask of 20 ⁇ m line and space pattern by a UV irradiation apparatus PLA-600FA manufactured by Canon Inc., and then at a temperature of 110 ° C.
• Post exposure heating (PEB) was performed on a hot plate for 120 seconds.
• the film was immersed in a 0.4% TMAH aqueous solution for 60 seconds for development, and then washed with running ultrapure water for 20 seconds.
• the obtained line and space pattern was immersed in PGMEA for 2 minutes. The case where the pattern completely disappeared was marked with ⁇ , and the case where the pattern remained was marked with ⁇ . Table 4 shows the obtained results.
• Comparative Example 1 and Comparative Example 2 sufficient water and anisole liquid repellency was not obtained after post-baking, and in Comparative Example 1, the liquid repellency was greatly reduced after UV-O 3 irradiation.
• Comparative Examples 3 and 4 reflow occurred during post-baking, and the pattern shape changed from a trapezoid to a semicircular shape.
• Comparative Example 5 lacked the storage stability and resulted in poor reworkability after post-baking.

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